Azo-dyestuffs containing {60 ,{62 -dichloropropionylamino or {60 ,{62 -dibromopropionylamino groups

ABSTRACT

Monoazo dyestuffs containing at least two and at most three sulfonic acid groups of the formula   WHEREIN D is unsubstituted o-sulfophenyl, unsubstituted osulfonaphthyl or such groups substituted by lower alkyl, lower alkoxy, phenoxy, trifluoromethyl, chlorine, bromine, phenylazo or sulfo, R&#39;&#39; is methyl or carboxy, R&#39;&#39;&#39;&#39; is hydrogen, phenyl sulfophenyl, disulfophenyl, sulfochlorophenyl, sulfodichlorophenyl, sulfonaphthyl, disulfonaphthyl, 2sulfostilbenyl, or 2,3-tetramethylene-4-sulfophenyl, X is Alpha , Beta -dichloropropionylamino or Alpha Beta dibromopropionylamino bound to a ring carbon atom of the benzene and naphthalene rings D and R&#39;&#39;&#39;&#39; and n is 1 or 2. Also provided are 1:2 or 1:1 chromium, cobalt or copper complexes of a monoazo dyestuff containing at least 2 and at most 3 sulfonic acid groups which dyestuff corresponding to the formula   WHEREIN R is unsubstituted o-hydroxybenzene, unsubstituted ohydroxynaphthalene or such groups substituted by lower alkyl, lower alkoxy, trifluoromethyl, chlorine, bromine or sulfo, R1 is   WHEREIN R&#39;&#39; is methyl or carboxy, R&#39;&#39;&#39;&#39; is hydrogen, phenyl, sulfophenyl, disulfophenyl, sulfochlorophenyl, sulfodichlorophenyl, sulfonaphthyl, disulfonaphthyl, 2sulfostilbenyl, or 2,3-tetramethylene-4-sulfophenyl, X is Alpha , Beta -dichloropropionylamino or Alpha , Beta dibromopropionylamino bound to a ring carbon atom of the benzene and naphthalene rings R and R&#39;&#39;&#39;&#39; and n is 1 or 2. Dyeings produced on cellulosic fibers with the dyestuffs of this invention are usually distinguished by the purity of their tints, by their good fastness to light and above all, by their excellent fastness to washing.

United States Patent n 1 De Montmollin et al.

[ 1 June 24, 1975 Inventors: Rene De Montmollin, Riehen; Henri Riat, Arlesheim, both of Sweden [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: June 1, 1972 [21] Appl. No.: 258,774

Related US. Application Data [60] Division of Ser. No. 876,069, Nov. 12, 1969, Pat. No. 3,755,390, which is a continuation-in-part of Ser. No. 753,829, Oct. 22, 1968, abandoned, which is a continuation of Ser. No. 608,710, Nov. 1, 1966, abandoned, which is a division of Ser. No. 305,539, Aug. 29, 1963, abandoned, which is a continuation-in-part of Ser. No. 731,097, April 28, 1958, abandoned.

[52] US. Cl 260/163; 8/41 R; 8/50; 260/147; 260/151; 260/154; 260/161;

[51] Int. Cl.... C0912 62/40; C09b 62/50; D06p l/38 Primary Examiner-Floyd D. Higel Allorney, Agent, or FirmWenderoth, Lind & Ponack [5 7] ABSTRACT Monoazo dyestuffs containing at least two and at most three sulfonic acid groups of the formula wherein D is unsubstituted o-sulfophenyl, unsubstituted o-sulfonaphthyl or such groups substituted by lower alkyl, lower alkoxy, phenoxy, trifluoromethyl, chlorine, bromine, phenylazo or sulfo, R is methyl or carboxy, R is hydrogen, phenyl sulfophenyl, disulfophenyl, sulfochlorophenyl, sulfodichlorophenyl, sulfonaphthyl, disulfonaphthyl, 2-sulfostilbenyl, or 2,3- tetramethylene-4-sulfophenyl, X is a,,6dichloropropionylamino or a,B-dibromopropionylamino bound to a ring carbon atom of the benzene and naphthalene rings D and R" and n is l or 2. Also provided are 1:2 or 1:1 chromium, cobalt or copper complexes of a monoazo dyestuff containing at least 2 and at most 3 sulfonic acid groups which dyestuff corresponding to the formula wherein R is unsubstituted o-hydroxybenzene, unsubstituted o-hydroxynaphthalene or such groups substituted by lower alkyl, lower alkoxy, trifluoromethyl, chlorine, bromine or sulfo, R, is

7 Claims, No Drawings AZO-DYESTUFFS CONTAINING a,B-DICHLOROPROP1ONYLAMINO OR a,B-DIBROMOPROPIONYLAMINO GROUPS CROSS-REFERENCES TO RELATED APPLICATIONS This is a division of application Ser. No. 876,069, filed Nov. 12, I969, (now U.S. Pat. No. 3,755,290) which application is a continuation-in-part application of our copending application Ser. No. 753829, filed July 22, 1968, now abandoned which was a streamlined continuation of our application Ser. No 608710, filed Nov. 1, 1966, now abandoned, which itself was a division of our application Ser. No. 305539, filed Aug. 29, 1963, now abandoned, which in turn was a continuation-in-part of our application Ser. No. 73l097, filed Apr. 28, 1958, now abandoned.

This invention provides valuable new water-soluble azo dyestuffs which contain at least one aromatically bound afi-dichloroor dibromopropionylamino group. More especially it provides o-sulfobenzene-o'-hydroxy or -o-aminomonoazo naphthalene dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound azB-dichloroor dibromopropionylamino groups, which dyestuffs may be further substituted in the benzene radical by lower alkyl, lower alkoxy, phenoxy, acetylamino, chlorine or bromine. Furthermore, it also provides benzenemonoazosulfonaphthalene dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound a:,B-dichloro or dibromo propionylamino groups, which dyestuffs may be further substituted in the benzene radical by amino. lower alkyl or lower alkoxy, The invention also provides o-sulfobenzene or sulfonaphthalenemonoazo pyrazolone dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound azB-dichloroor -dibromopropionylamino groups, which dyestuffs may be further substituted in the diazo component by lower alkyl, lower alkoxy, phenoxy, acylamino other than a,fi-dihalogenpropionylamino, chlorine or bromine and in which dyestuffs the coupling component is a 3-methylor 3-carboxy-5-pyrazolone bound to the azo-linkage in 4-position.

Included in the invention are moreover complex chromium, cobalt or copper compounds of monoazo dyestuffs containing at least two and at most three sulfonic acid groups and at least one and at most two aromatically bound azB-dichloroor -dibromopropionylamino groups, which dyestuffs correspond to the formula wherein R is the radical of an o-hydroxybenzene or an o-hydroxynaphthalene which may be further substituted by lower alkyl, lower alkoxy, acylamino other than a,B-dihalogenopropionylamino, chlorine or bromine and R is the radical of a hydroxyor aminonaphthalene bound to the azolinkage in o-position to a hydroxy or amino group or the radical of a 3-methylor 3-carboxy-5-pyrazolone bound to the azo-linkage in 4- position. Further complexes falling within this invention are chromium, cobalt or copper complexes of monoazodyestuffs containing at least two and at most three sulfonic acid groups and corresponding to the formula HO NH HOS wherein R is an o-sulfobenzene radical which may be further substituted by lower alkyl, lower alkoxy, trifluoromethyl, chlorine or bromine, one X is hydrogen and the other X is a sulfonic acid group and R is a benzene radical which may be substituted by lower alkyl, trifluoromethyl, chlorine or bromine, sulfo or nitro. In the above definition the term lower" means: containing up to 4 carbon atoms".

Especially valuable groups of such dyestuffs are e.g.:

l. Dyestuffs of the general formula A 5 if HOS wherein A stands for a,B-dichloroor dibromopropionyl, R for hydrogen or an optionally substituted lower alkyl radical, and D, for the radical of a diazo component which contains at least one sulfonic acid group and which also may contain an azB-dichloroor dibromopropionylamino group.

Valuable are e.g. diazo components in which the radical D, has the formula SOH OH 3 S A-HN SOH

3 SO3H 30 1i so H CH s0 303R G OH3COHN- NHC OCH=CH 2. Dyestuffs of the general formula wherein A has the aforecited meaning, one Y stands for hydrogen and the other for a sulfonic acid group, and D stands for the radical of a diazo component which may contain one water-solubilizing group, e.g.

or especially diazo components as mentioned above,

which contain an azB-dichloroor dibromopropionylamino group and/or a sulfo group.

3. Dyestuffs of the general formula N= N... D "G! A wherein A and R possess the aforecited meanings, D stands for the radical of a diazo component which contains at least two sulfonic acid groups and may contain further substituents such as azo groups, especially the radicals H0 8 SO H so it so H 3 and wherein the benzene nucleus Z may contain fur- 4. Monoazo dyestuffs with at least two sulfonic acid groups of the general formula wherein A possesses the aforecited meaning, D stands for the radical of a diazo component, e.g.

SOH SOH so a whereby the sulfonic acid group is in ortho-position to the azo group, and K, stands for the radical of a hydroxynaphthalenesulfonic acid which may be further substituted, e.g.

I I I 803K HO OH i I so H CH 3 3 Ho NHcocH H 0 s HO NHCOCH3 H H038 so 3 NC0CH2C1 H0 3 5 6 or a ketomethylene compound e.g. and K for the radical of a coupling compound which CH couples in the adjacent position to an enolizable keto I 3 c1 group, e.g. O=N

5 i l 3 3 CHGO l Cl O=-=-N\ H l 3 m cH00 Q so H I CH=CH NHCOCH 3 CH -CHCO I 3 7 SO H H0 8 CH T 0 3 S0311 l -cac0 coon N C N (JO- 3H I SO H CHCO 5. Dyestuffs of general formula 1) -N=N-K -N-A and the dyestuff itself contains at least two sulfonic acid 5 2 groups.

R 6. Metal complex compounds of monoazo dyestuffs h A d R th f d D having at least two acid-solubilizing groups and at least a i i e a Greene z gl g 5 one a,B-dichloroor dibromopropionylamino group. s an S or e m 0 a law componen w m Suitable metal atoms are chromium, cobalt, nickel,

tains at least one sulfonic acid group and may contain and copper atoms the lastmamed being preferred an azo group, e.g. The choice of diazo components for building dye- SO'ISH COOH H stufis of this type includes Z-aminol I 3 hydroxybenzenes, l-amino-Z-hydroxyand Z-amino-lhydroxynaphthalenes, and 2-aminobenzenel 40 carboxylic acids. Examples of suitable coupling compounds are l-(amino)aryl-S-pyrazolones and aminohy- S0 H I droxynaphthalenesulfonic acids 3 The afi-dichloroor dibromo propionyl radical may so H be attached to the coupling compound, for instance in so H the following combination:

so v N:

A HO N- AW wherein R and A have the aforecited meanings, or alternatively to the diazo component, e.g.:

In addition the a,B-dichloroor dibromopropionyl NH-A radical may be attached to both the diazo-component and the coupling-component, e.g. in the following combination A-HN c 0 wherein A and R possess the aforecited meanings.

Naturally 2:1 metal complexes as well as 1:1 complexes can be produced. The former contain preferably chromium or cobalt metal atoms.

The invention provides monoazo dyestuffs containing at least two and at most three sulfonic acid groups of the formula wherein D is unsubstituted o-sulfophenyl, unsubstituted o-sulfonaphthyl or such groups substituted by lower alkyl, lower alkoxy, phenoxy trifluoromethyl, chlorine, bromine, phenylazo or sulfo, R' is methyl or carboxy, R" is hydrogen, phenyl, sulfophenyl, disulfophenyl sulfochlorophenyl, sulfodichlorophenyl, sulfonaphthyl, disulfonaphthyl, 2-sulfostilbenyl, or 2,3- tetramethylene-4-sulfophenyl, X is a,,8-dichloropropionylamino or a,/3-dibromopropionylamino bound to a ring carbon atom of the benzene and naphthalene rings D and R and n is l or 2. Also provided are 1:2 or 1:1 chromium, cobalt or copper complexes of a monoazo dyestuff containing at least 2 and at most 3 sulfonic acid groups which dyestuff corresponding to the formula RN N-R wherein R is unsubstituted o-hydroxybenzene, unsubstituted o-hydroxynaphthalene or such groups substituted by lower alkyl, lower alkoxy, trifluoromethyl, chlorine, bromine or sulfo, R, is

wherein R is methyl or carboxy, R" is hydrogen, phenyl, sulfophenyl, disulfophenyl, sulfochlorophenyl, sulfodichlorophenyl, sulfonaphthyl, disulfonaphthyl, 2- sulfostilbenyl, or 2,3-tetramethylene-4-sulfophenyl, X is a,B-dichloropropionylamino or a,B-dibromopropionylamino bound to a ring carbon atom of the benzene and naphthalene rings R and R" and n is l or 2. The invention in addition provides monoazo dyestuffs containing 2 or 3 sulfonic acid groups and corresponding to the formula wherein one W is hydrogen or sulfo, the other W is a,B-dichloropropionylamino or a,B-dibromopropionylamino and W is hydrogen or, if the W in 0- position to W, is hydrogen, W, is hydrogen or sulfo and K is wherein R is methyl or carboxy and R is hydrogen, phenyl, sulfophenyl, disulfophenyl, sulfochlorophenyl, sulfodichlorophenyl, sulfonaphthyl or disulfonaphthyl.

The dyestuffs of this invention may be obtained from dyestuff components which already contain the dihalogenated propionyl radical. Such dyestuff components are obtainable by methods in themselves known, for example, by the acylation of appropriate compounds with a halide or anhydride of an azB-dihalogen-propionic acid.

Suitable compounds for this purpose are those which contain an easily acylatable amino group, for example, a monoalkylamino group or a primary amino group, and in the case of diam-components, a less easily acylatably primary amino group, and in the case of coupling components either a less easily acylatable amino group or a hydroxyl group responsible for coupling. As amino groups that are less readily acylated there may be mentioned principally those which occupy a position vicinal to an acid group, for example, a sulfonic acid group. Aminohydroxy-compounds are acylated in such manner that esterification of the hydroxyl group is avoided.

instead of introducing the aforesaid radicals into the dyestuff components before the dyestuff is made, they may be introduced into the finished dyestuffs. Thus, valuable dyestuffs containing an azB-dichloroor dibromopropionylamino group can be obtained by reacting a dyestuff which contains an acylatable amino group, and above all a free amino group, with, for example, a:B-dichloroor dibromopropionic acid chloride or anhydride.

As soluble organic dyestuffs, which can be made in the above manner, there may be used metal-free or metalliferous monoazoand disazo-dyestuffs which latter may also be prepared by metallisation. Especially good results are obtained with soluble azodyestuffs which possess no affinity for cotton or at most no pronounced affinity therefor. Such amino-azo-dyestuffs may be obtained e.g. by hydrolysis of acylamino-azo dyestuffs, by reduction of the nitro groups of nitro-azodyestuffs or by coupling a diazotized aromatic amine with a coupling component containing an acylatable amino group.

As amines which, after diazotation, may be used as diazo components to produce monoand disazo dyestuffs for use of the process of this invention, there may be mentioned for example:

aminobenzene, 1-amino-2(3 or 4)-methylbenzene,

1-amino-4-methoxybenzene-Z-sulfonic acid,

1-aminobenzene-2(3 or 4)-sulfonic acid,

l-aminbenzene-2,5 (or 2,4)-disulfonic acid, 3 (or 4 )-nitrol -aminobenzene, 4-nitro-1- aminobenzene-Z-sulfonic acid,

4 (or )acetylaminol-aminobenzene-2-sulfonic acid, 4- (or 3) acetylamino-l-aminobenzene,

4 (or 5)-nitro-2-hydroxy-l-aminobenzene,

6-acetylamino-2-hydroxy- 1 -aminobenzene-5- sulfonic acid,

Z-hydroxy-l-aminobenzene-4 (or 5)-sulfonic acid,

2 (3 or 4)-aminobenzoic acid,

4-chloracetylamino-1-aminobenzene-2-sulfonic acid,

4 B-Chlorpropionylaminol -aminobenzene-2- sulfonic acid, 3-trifluoromethyl-l-aminobenzene-6-sulfonic 3-trifluoromethyl-o-phenoxy-l-aminobenzene, methoxy-l-aminobenzene-2-sulfonic acid, 1-aminoazobenzene2,4'-disulfonic acid, 4,4'-diaminodiphenyl-2,2' (or 3,3')-disulfonic acid, l-amino-4-methyl (chloro-, bromoor phenoxy)-benzene-6-sulfonic acid, l-aminonaphthalene-3,6disulfonic acid, 2-aminonaphthalene-6,S-disulfonic acid, 2-aminonaphthalene-l-sulfonic acid, 4,4-diamino-5,5'-dimethyldiphenyl-2,2'-disulfonic acid,

2-amino-4 (or diphenylsulfone, l-aminonaphthalene-4 (5, 6 or 7)-sulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-4,6,8-trisulfonic acid,

Z-aminonaphthalene-l (4, 6, 7 or 8)-sulfonic acid.

Of special value are diazotisable amines containing an a,B-dichloroor dibromopropionylamino group, e.g.

l-amino-3 (or 4)-dicl1loro (or dibromo)- propionylaminobenzene-o-sulfonic acid, 1-amino-3-dichloro (or dibromo)-propionylamino-4- chloro (methyl or methoxy)-6sulfonic acid, l-amino-4-dichloro (or dibromo)-propionylaminobenzene-2,5 (or 2,6-disulfonic acid and l-amino-3-dichl0ro (or dibromo propionylaminobenzene-4,6-disulfonic acid.

As coupling components which may be used to produce monoor disazodyestuffs for use of the process of this invention, ther may be mentioned:

acid, 4.

5 )-acetylamino-4 '-methyl-1 :l

aminobenzene,

3-acetylaminol -aminobenzene,

3-methoxyl-aminobenzene,

3-dichloropropionylaminol -aminobenzene,

S-methoxy-Z-methyll-aminobenzene,

l-amino-2-methoxybenzene,

N-ethyl-N-benzylphenylamino-sulfonic acid,

l,3-diaminobenzene-6-sulfonic acid,

meta-toluidine, 3-aminophenyl urea,

3-methyl-5-pyrazolone,

l-( 2'-methyl-6'-chlorophenyl )-3-methyl-5- pyrazolone,

3-carboxy-5-pyrazolone,

1 -phenyl-3 -methyl-5-pyrazolone,

1-[2-(or 3' or 4')-chlorophenyl1-3-methyl-5- pyrazolone, 1-[3' (or -4')-aminophenyl]-3-carboxy-5- pyrazolone, 1-[2-(or 3" or 4')-sulfophenyl]-3-methyl-5- pyrazolone,

l-(2'-chloro-5'-sulfophenyl)-3-methyl-5-pyrazolone,

l-(2,5'-dichloro-4'-sulfophenyl)-3-methyl-5- pyrazolone,

barbituric acid,

acetoacetic acid ortho-anisidide,

l-aminonaphthalene-4 (5, 6, 7 or 8)-sulfonic acid,

1- or 2-hydroxynaphthalene,

l-hydroxynaphthalene-4 (or 5)-sulfonic acid,

2-hydroxynaphthalene-4(6, 7 or 8)-sulfonic acid, 2-hydroxynaphthalene-3,6 (5,7 or 6,8)-disulfonic acid,

2-aminonaphthalene-5 (6, 7 or 8)-sulfonic acid,

1-amino-8-hydroxynaphthalene-4,6-disulfonic acid,

l-hydroxynaphthalene-3,6(or 4,8)-disulfonic acid, 2N-methylaminonaphthalene-6 (7 or Ell-sulfonic acid,

Z-amino-8-hydroxynaphthalene-6-sulfonic acid,

2-N-methylamino-S-hydroxynaphthalene-fi-sulfonic acid l-amino-S-hydroxynaphthalene-3,6-disulfonic acid,

Z-amino-S-hydroxynaphthalene-7-sulfonic acid,

2-N-methylamino-S-hydroxynaphthalene-7-sulfonic acid,

2-phenylamino-8-hydroxynaphthalene- 3 ,6-

disulfonic acid,

2'N-( 3 -carboxyphenyl )amino-S- hydroxynaphthalene-7-sulfonic acid,

l-benzoylamino-S-hydroxynaphthalene-3,6 (or 4,6)-

disulfonic acid 2-ureido-5-hydroxynaphthalene-7-sulfonic acid, 2-carbethoxyamino-5-hydroxynaphthalene-7- sulfonic acid,

2-B-methoxycarbethoxyamino-S- hydroxynaphthalene-7-sulfonic acid,

I-( n-butyrylamino )-8-hydroxynaphthalene-3 ,6( or 4,6)-disulfonic acid 1-acryloylamino-8-l1ydroxynaphthalene-3,6(or 4,6)-

disulfonic acid 1-fi-chloropropionylamino-S-hydroxynaphthalene- 3,6(or 4,6)-disulfonic acid 1-chloroacetylamino-8-hydroxynaphthalene-3,6(or

4,6)-disulfonic acid.

As examples of dyestuffs containing acylatable amino groups for use in the process of this invention, to be acylated, for example, with a dichloro or dibromopropionic acid halide or a corresponding acid anhydride, there may be mentioned the following (the acylatable azo )--pyrazolone-4',4",8 -trisulfonic acid (orange),

l-amino-2-( 4'-amino)-phenylazo-7-phenylazo-8- hydroxynaphthalene-3,6,4 '-trisulfonic acid (greenish black), 4-amino-4'-(4"-methoxy)-naphthyl-( l azoslilbene-2,2-disulfonic acid (orange), l-(4 -amino)-benzoylamino-7-phenylazo-8-hydroxynaphthalene-3,6,2"-trisulfonic acid (blue-red),

Copper complex compound of l-hydroxy-2-(2- hydroxy-S'-methyl)-phenylazo-6-aminonaphthalene-3,4-disulfonic acid (violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy)-naphthyl-( l ')-azo-6-amino-naphthalene- 3,4'-disulfonic acid (blue),

Copper complex compound of l-(2'-hydroxy-3'- amino)-phenylazo-2-hydroxy-naphthalene-6,5 disulfonic acid (blue-violet),

Nickel complex compound of 1-hydroxy-2-(2'- hydroxy)-phenylazo- 6-amino-naphthalene-3,3',S'- trisulfonic acid (red-brown),

lz2-chromium complex compound of l-hydroxy-Z- (2'-hydroxy-3'-chloro)-phenylazo-6-aminonaphthalene-3,5'-disulfonic acid (navy-blue),

lz2-cobalt complex compound of l-phenyl-S-rnethyl- 4-(2"-hydroxy-3"-amino)-phenylazo-5- pyrazolone-4',5"-disulfonic acid (brown),

Mixed l:2-chromium complex compound of l-(2'- hydroxy-3'-cl1loro)-phenylazo-2-hydroxy-8- acetylamino-naphthalene-S'-sulfonic acid and lhydroxy-2-( 2 '-hydroxy-3 '-chloro )-phenylazo-6- aminonaphthalene-3,5'-disulphonic acid (navy blue),

Mixed lz2-chromium complex compound of l-(2'- hydroxy-5 '-chloro )-phenylazo-2-hydroxy-8- acetylamino-naphthalene-3-sulfonic acid and lhydroxy-2-(2'-hydroxy-5'-chloro)-phenylazo-6- amino-naphthalene-3,3'-disulfonic acid (navyblue),

:Z-chromium complex compound of l-hydroxy-Z- (2 '-hyd roxy-5 '-chloro )-phenylazo-6-aminonaphthalene-3,3-disulfonic acid (navy-blue),

:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-S '-chloro )-phenylazo-6-aminonaphthalene-3,3-disulfonic acid (brown-violet),

:2-cobalt complex compound of l-hydroxy-2-(2'- hydroxy-3'-chloro)-phenylazo-6-aminonaphthalene-3,5 '-disulfonic acid (brown-violet),

:2-chromium complex compound of l-hydroxy-2- (2 '-hydroxy-5 '-nitro )phenylazo-6-aminonaphthalene-3,3-disulfonic acid (navy-blue),

:2-cobalt complex compound of l-hydroxy-2-(2'- hydroxy-S -nitro )-phenylazo-6-aminonaphthalene-3,3 '-disulfonic acid brown),

:Z-chromium complex compound of l-hydroxy-2- (2-hydroxy-3'-nitro)-phenylazo-6-aminonaphthalene-3,5'-disulfonic acid (navy-blue),

:Z-cobalt complex compound of l-hydroxy-2-(2- hydroxy-3 '-nitro )-phenylazo-6-amino naphthalene-3,5'-disulfonic acid (brown-violet),

(violettishlz2-chromium complex compound of hydroxy)-phenylazo-2-hydroxy-8-aminonaphthalene-3,5'-disulfonic acid (gray),

lz2-chromium complex compound of 1-hydroxy-2- (2'-hydroxy-6'-nitro)-naphthyl-( l )-azo-6-aminonaphthalene3,4'-disulfonic acid (navy-blu ,l,

1:2-cobalt complex compound of l-hydro. ,-2-(2'- hydroxy-6-nitro)-naphthyl-( l )-azo-6-aminonaphthalene-3,4'-disulfonic acid (brown-violet),

Mixed lz2-chromium complex compound of l-(2'- hydroxy-3 '-nitro )-phenylazo-Z-hydroXy-S-aminonaphthalene-5'-sulfonic acid and l-hydroxy-2-(2'- hydroxy-3 '-chloro )-phenylazo-6- aminonaphthalene-3,5-disulfonic blue),

1:2-chromium complex compound of l-hydroxy-2- (2 '-hydroxy)-naphthyl-( 1 ')-azo-6-aminonaphthalene-3,4'-disulfonic acid (navy-blue),

l -l1ydroxy-2-( 3 -amino )-phenylazo-naphthalene- 4,6,6'-trisulfonic acid (red),

l-hydroxy-2-(3'-amino)-phenylazo-naphthalene- 4,7,6-trisulfonic acid (red),

l-hydroxy-2-(3'-amino)-phenylazo-naphthalene- 3,6,6'-trisulfonic acid-8-sulfonic acid amide (bluered),

Copper complex compound of l-hydroxy-2-(2'- hydroxy)-phenylazo-8-amino-naphthalene-3 ,6,5 trisulfonic acid (blue-violet),

Nickel complex compound of l-hydroxy-2-(2'- hydroxy)-phenylazo-8-amino-naphthalene-3,6,5 trisulfonic acid (violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy-S '-cl1loro )-phenylazo-8-aminonaphthalene-3,6,3'-trisulfonic aicd (blue-violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy-3'-chloro)-phenylazo-8-aminonaphthalene-3,6,5'-trisulfonic acid (blue-violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy-S '-methylsulfonyl)-phenylazo-8-aminonaphthalene-3,o-disulfonic acid (violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy)-phenylazo-8-amino-naphthalene-3,6- disulfonic acid-5'-sulfonic acid amide (blueviolet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy)-phenylazo-8-amino-naphthalene-3 ,5 ,5 trisulfonic acid (violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy-S '-methylsulfonyl)-phenylazo-8-aminonaphthalene-3,S-disulfonic acid (violet),

Copper complex compound of l-hydroxy-(2- hydroxy-3 -carboxy )-phenylazo-8-aminonaphthalene-3,6,5-trisulfonic acid (blue-violet),

Copper complex compound of l-hydroxy-2-(2'- hydroxy-3 '-carboxy )-phenylazo-8-aminonaphthalene-3,5,5-trisulfonic acid (violet),

l-amino-7-phenylazo-8-hydroxynaphthalene-3,6,3

trisulfonic acid (bluish-red),

2-(4'-amino)-phenylazonaphthalene-4,6,8-

trisulfonic acid (orange),

l-(2',5'-dichloro)-phenyl-3-methyl-4-(3"-amino) phenylazo-S-pyrazolone-4,6"-disulfonic acid (yellow),

l-amino-7-phenylazo-8-hydroxynaphthalene-3 ,6 ,2

trisulfonic acid (blue-red),

acid (navyaminonaphthalene-3,6,6'-trisulfonic acid (bluered),

l -hydroxy-2-( 3-amino )-phenylazo-8-( 3 '-amino)- benzoylaminonaphthalene-3,6,6'-trisulfonic (blue-red),

l-hydroxy-2-(3-amino)-phenylazo-7-(3"-amino)- phenylazo-S-amino-naphthalene-3,6,6',6"-tetrasulfonic acid (blue-gray),

1-hydroxy-2-(4'amino)-phenylazo-7-(4"-amino)- phenylazo-S-amino-naphthalene-3,6,2',2"-tetrasulfonic acid (greenish black), 1-hydroxy-2 (3-amino)-phenylazo-8-(4"-amino)- benzoylaminonaphthalene-3,6,6'-trisulfonic acid (blue-red),

l:2-chromium complex compound of l-hydroxy-2- (2'-hydroxy-5'-nitro)-phenylazo-8- aminonaphthalene-3,o-disulfonic acid (greenish black),

l:2-chromium complex compound of l-hydroxy2- (2-hydroxy-5-chloro)-phenylazo-8- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-chromium complex compound of l-hydroxy-Z- (2 '-hydroxy-4'-nitro-5 '-chloro)-phenylazo-8- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-chromium complex compound of l-hydroxy-2- (2'-hydroxy-3'-chloro-5'-nitro)-phenyla2o-8- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-chromium complex compound of l-hydroxy-Z- (2-hydroxy-3 '-nitro-5'-chloro )-phenylazo-8- aminonaphthalene-3,o-disulfonic acid (navy-blue),

1:2-chromium complex compound of l-hydroxy-2- (2-hydroxy-3 ,5 '-dinitro)-phenylazo-8- aminonaphthalene-3,o-disulfonic acid (greenish black).

l:2-cobalt complex compound of l-hydroxy-2-(2'- hydroxy-S'-chloro)-phenylazo-8- aminonaphthalene-3,o-disulfonic acid (navy-blue),

lz2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-4'-r1itro-5 '-chloro )-phenylazo-8- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-3 -chloro-5 '-nitro )-phenylazo-8- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-3 -nitro-5 '-chloro)-phenylazo-8- aminonaphthalene-3,G-disulfonic acid (navy-blue),

l:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-3 ,5 -dinitro )-phenylazo-8- aminonapthalene-3,6-disulfonic black),

l:2-chromium complex compound of 1-hydroxy-2- (2'-hydroxy-5-nitro)-phenylazo-8- aminonaphthalene-3,S-disulfonic acid (navy-blue),

l:2-chromium complex compound of l-hydroxy-2- (2'-hydroxy-5 '-chloro )-phenylazo-8- amin0naphthalene-3,S-disulfonic acid (navy-blue),

1:2-chromium complex compound of l-hydroxy-Z- (2-hydroxy-5'-nitro)-phenylazo-7- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-chromium complex compound of l-hydroxy-2- (2'-hydroxy-5'-chloro)-phenylazo-7- aminonaphthalene-3,6-disulfonic acid (navy-blue),

l:2-chromium complex compound of l-hydroxy-Z- (2 '-hyd roxy-S '-chloro )-phenylaz0-8- aminonaphthalene-S,7-disulfonic acid (navy-blue),

acid

acid (bluish l:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-S'-nitro)-phenylazo-8-aminonaphthalene- 3,5-disulfonic acid (navy-blue),

l:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-S '-chloro)-phenylazo-8- aminonaphthalene-3,S-disulfonic acid (na' blue),

l:2-cobalt complex compound of l-hydro/ 2-(2'- hydroxy-S '-nitro )-phenylazo-7-aminonaphthalene- 3,6-disulfonic acid (navy-blue),

l:2-cobalt complex compound of l-hydroxy-2-(2- hydroxy-S '-chloro)-phenylazo-7- aminonaphthalene-3,o-disulfonic acid (navy-blue),

l:2-cobalt complex compound of l-hydroxy-2-(2'- hydroxy-S"chloro)-phenylazo-8- aminonaphthalene-S,7-disulfonic acid (navy-blue),

Copper complex compound of l-hydroxy-2-( l hydroxy )-naphthyl-( 2 )-azo-8-aminonaphthalene- 3,6,6'-trisulfonic acid (reddish blue),

Copper complex compound of l-hydroxy-2-( l hydroxy)-naphthyl-(2')-azo-8-aminonaphthalene- 3,6,8-trisulfonic acid (reddish blue),

Copper complex compound of l-hydroxy-2-( l hydroxy)naphthyl-(2')-azo-8-aminonaphthalene- 3,6,4'-trisulfonic acid (blue),

Copper complex compound of l-hydroxy-2-( l hydroxy)-naphthyl-(2)-azo-8-aminonaphthalene- 5,4',8-trisulfonic acid (blue),

Copper complex compound of l-hydroxy-2-( l hydroxy)-naphthyl-(2')-azo-8-aminonaphthalene- 3,6,5'-trisulfonic acid (reddish blue),

Copper complex compound of l-phenyl-3-methyl-4- (2"-hydroxy-6"-amino)-naphthyl-( l ')-azo-5- pyrazolone-2',4',4"-trisulfonic acid (yellowish brown),

:2-cobalt complex compound of l-phenyl-3-methyl- 4-( 2 "-hydroxy-3 "-amino )-phenylazo-5- pyrazolone-4',5"-disulfonic acid brown),

:Z-cobalt complex compound of l-(2',5'-dichloro)- phenyl-3-methyl-4-( 2 '-hydroxy-3 "-amino)- phenylazo-5-pyrazolone-4,5'-trisulfonic acid (yellowish brown),

:2-cobalt complex compound of l-phenyl-3-methyl- 4-(2"-hydroxy-3"-amino-S-nitro)-phenylazo-5- pyrazolone-Z',5'-disulfonic acid (yellowish brown),

:2-cobalt complex compound of 1-(2',5'-dichloro)- phenyl-3-methyl-4-(2"-hydroxy-6"-amino)- naphthyl-( 1' )-azo-5-pyrazolone-4 ,4 '-disulfonic acid (brown),

:2-chromium complex compound of l-phenyl-3- methyl-4-(2"-hydroxy-3"-amino)-phenylazo-5- pyrazolone-4',5"-disulfonic acid (orange-red),

:Z-chromium complex compound of l-(2',5'-

dichloro)-phenyl-3-methyl-4-(2"-hydroxy-3"- amino )-phenylazo-5 -pyrazolone-4 ',5 '-trisulfonic acid (orange),

:2-chromium complex compound of l-phenyl-3- methyl-4-(2"-hydroxy-3"-amino-5'-nitro)- (yellowish phenylazo-S-pyrazolone-Z ,5 -disulfonic acid (orange),

l-hydroxy-2-( 4 '-methoxy )-phenylazol methylamino-naphthalene-3 ,2 '-disulfonic acid l-hydroxy-2-phenylazo-6-ethylamino-naphthalene- 3,2',5 '-trisulfonic acid (scarlet),

23 24 l-phenyl3-methyl-4-[4-(4'"-amino-2"'-methyl)- hydroxy-8-amino)-naphthyl-(2")-azo-2,2-

phenyl-3 '-methyl l-phenylazo-5-pyrazolonedimethyl-l ,l '-diphenyl-5,3 ,6 -trisulfonic acid 2',5,6"-trisulfonic acid (reddish yellow), (red-violet), 4-amino-4'-(4'-methoxy)-phenylazo-stilbene-2.2'- "-a y )-p y azo-4'-(2"- disulfonig id hydroxy)-naphthyl-(1"')azo-l,1'-d|phenyl-5,3"'- l-naphthyl-(2')-3-methyl-4-[4"-(4"-amino)- tetrasulfonic i (r d) phenyl]-phenylazo-5-pyrazolone-4',8',2"- The acylation of such a dyestuff containing an acylatri lf i id (browmorange), table amino group with one of the aforesaid dihalogen- 1. 3 h 4 4" 3"' propionic acid halides or anhydrides isadvan tageously 3'u -5 z',4', 10 carried out m the presence of an acldblndll'lg agent u-isulfonic acid (oranggbrown), such as sodium acetate, sodium hydroxide or sodium 1- h 3- h 4 [4" 4"' i h hydrogen carbonate and underrelatively mild condi- 2" 5' 5 trons, for example, In an organic solvent or at a rela- 2"5"2"' t i lf i acid (orangebrowm tlvely low temperature In an aque0us medium. lmaphthyba, n m The dyestuffs of th s invention are new. They are suitphenylazo 3mmethy]l phenylazo 5 pyram|0ne able for dyeing or printing especially polyhyd roxylate d 4' 8"2"' t i |f i acid (orangebrown), materials of fibrous structure such as cellulosic materl- 2' als, and also synthetic fibers, for example, of regenerphenylazo 3I, methyll phenylazo s pyraz0lonc ated cellulose, or natural materials, for example, cellu- 5i7izm trisulfonic acid (orangebmwn), lose, linen or above all cotton. They are suitable for i m dyelng by the so-called direct dyeing methods and also by printing or foularding dyeing methods, especially from aqueous alkaline solutions, which may contain a high content of salts, for example, by the process in which the dyestuff is fixed on the material to be dyed by a heat treatment, for example, by steaming, in the presence of an alkali, or preferably by storing the dyed or printed material at room temperature or at a slightly elevated temperature, eg at a temperature between 15 and C for l to 24 hours according to the socalled cold-pad-batch-process. Due to the reactive dihalogenopropionylamino substituent a chemical bonding is formed between the chromophore of the azo dyestuff and the cellulosic fiber during the fixation process.

In order to remove non-fixed dyestuff and to improve the properties of wet fastness of the dyeings so produced on cellulose fibers the dyeings are thoroughly rinsed with cold and hot water. Advantageously they may also be treated with a dilute and advantageously slightly alkaline boiling solution of a nonionic detergent or a dispersing agent for a short time, for example,

phenylazo)-phenylazo-S-pyrazolone- 2',2' ,2 ,4' '-tetrasulfonic acid (orange-brown), lhydroxy-2-(4'-phenylazo)-7-amino-naphthalene- 3,2',4"-trisulfonic acid (blue-red), l-(4-aminc-2'-methylsulfonylamino )-phenylazo-3- methyl-4-phenylazobenzene-2",4"-disulfonic acid (orange-brown l-(4'-aminc-2'-sulfoacetylamino)-phenylazo-3- 3O methyl-4-phenylazobenzene-2",4"-disulfonic acid (orange-brown), 2-[4'-(4"-amino)-naphthyl-( l )-azo]- phenylazonaphthalene-4,6,8,7 '-tetrasulfonic acid (orange-brown), 35 2-[ 4-(4"-amino-3"-ethoxy )-naphthyl-( l )-azo]- phenylazonaphthalene-4,8,3'-trisulfonic acid (orange-brown 2-[4'-(1"-hydroxy-6"-amino)-naphthyl-(2")-azo- 2'-methy|1-phenylazonaphthalene-6,8,3'- 4O trisulfonic acid (blue-red), l-[4'-( l "-hydroxy-6"-amino)-naphthyl-(2")-az0]- naphthyl-( l ')-azobenzene-4,7',3"-trisulfonic acid 540 minutes (blue-Violet), Dyeings produced on cellulosic fibers with the dye- 'l P Y 1 Y stuffs of this invention are usually distinguished by the p y -l 'li fi"'" acid purity of their tints, by their good fastness to light and above all by their excellent fastness to washing. y )-P y The following Examples illustrate the invention, the

y yl' p y '"l' i parts and percentages being by weight: diphenyl-6,6,4'-trisulfonic acid (red), 4-(4"-amino-3"-methoxy-6"-methyl)-phenylazo-4'- EXAMPLE 1 l "'-hydroxy)-naphthyl-( p y 10.44 parts of the dyestuff of the formula are neutralized with sodium carbonate in 350 parts of water, and 3.4 parts of sodium bicarbonate are added. While stirring vigorously, a solution of 4.8 parts of wB-dichloropropionyl chloride in 10 parts of toluene is added dropwise at O-5C within l minutes. After /2 hour the new dyestuff formed is salted out with 100 parts of sodium chloride, filtered off and dried in vacuo at 5 to 60C.

The dyestuff dye cotton greenish yellow tints by the process described in Example 13.

When the above dyestuffis acylated with 7.5 parts of azB-dibromopropionyl chloride instead of 4.8 parts of azB-dichloropropionyl chloride, a product is obtained which likewise dyes cotton fast greenish yellow tints.

EXAMPLE 2 8.76 parts of the dyestuff of the formula EXAMPLE 3 5. l 8 parts of the dyestuff of the formula HO NH a n- -u :n-

0 no s- -SO3H s a are neutralized with sodium carbonate in 300 parts of water, and this solution is mixed at room temperature dropwise with a solution of 10 parts of azB-dichloropropionyl chloride in 15 parts of acetone, and by the simultaneous dropwise addition of aqueous sodium carbonate solution the pH value of the solution is maintained between 7 and 8. After complete acylation of the two amino groups the dyestuff is salted out with 100 parts of sodium chloride and dried in vacuo at to C. The dyestuff dyes cotton bluish-red tints.

By acylating the aminoazo dyestuffs in Column with azB-dichlorpropionyl chloride as described in the preceding Examples further dyestuffs are obtained that dye cotton the tints shown in Column ll.

30 B in N H 50 OCH -m: n- G-rm imcocn reddish yellow reddish yellow yellow -CH Oil- 1 Continued II -n:n I coon greenish yellow 3 greenish yellow reddlz sh orange -NH ao s- G -n 1:- Q

sou-lat -N==!I- 4811 yellow orange mwocn Continued I II H NR V A I, C Hr-N (3 greenish black z-zo sl 450 les, but with an equivalent amount of azB-dibromo- By acylatmg the ammoazodyestuffs of Column l of m the following table as described in the preceeding Expropmnylchlonqe further.dyestuffs are Obtamed that dye cotton the nns shown m Column 1] I II 80 E OH =N 7 m scarlet 0 0H m2 red $03K OH cu CH 1? 3 NH scarlet OH H0 S $0 11 011 I 18 CH l 3 l N=N CH I HN I scar- NH let (won H N NH 2 5 S c=n 2 N=N-c- ()H n reddish H yellow Z 2 2 2o Q= reddish yellow SO I 3 NR SO H I 0H 01-1 C N=N N=N 21 S0 11 H038 $03K scarlet Continued V s a 22 110 3-0- =N argue brown EXAMPLE 4 53.0 parts of the dyestuff of the formula OH IO ewe HZN 110 s are neutralized with sodium carbonate in 750 parts of water. 12 parts by volume of ION-sodium hydroxide solution and 120 parts by volume of a sodium chromesalicylate solution (containing 2.8 parts of chromium in 100 parts by volume) are added. and the mixture is refluxed for 3 hours. After cooling, the solution of the lz2-chromium complex so formed is neutralized with hydrochloric acid.

The above solution is cooled to 0 to 5C and parts 40 of anhydrous sodium acetate are added. While stirring vigorously, 40 parts of azB-dichloropropionyl chloride are added dropwise at 0 to 5C within 40 minutes. After 2 hours the solution is neutralized with sodium carbonate, and the dyestuff is salted out with sodium chloride and filtered off.

The dyestuff dyes cotton reddish grey tints.

The parent dyestuff of the above formula is obtainable, for example, by coupling diazotized 5-nitro-2- aminophenol with Z-phenylamino-S- hydroxynaphthalene-3z-disulfonic acid and reducing the nitro group in the resulting dyestuff to an amino group by means of sodium hydrosulfide.

EXAMPLE 5 43.9 parts of the dyestuff of the formula no sare neutralized with sodium carbonate in 500 parts of water. 12 parts by volume of ION-sodium hydroxide solution and 310 parts by volume of a cobalt sulfate solution of 5 percent strength are added, and the mixture is heated for 9% hour at to C. The solution of the lz2-cobalt complex obtained in this manner is allowed to cool and then adjusted to pH=7.

35 parts of anhydrous sodium acetate are added to the above solution which is then cooled to 0 to 5C, and at that temperature, while stirring vigorously, a solution of 35 parts of azB-dichloropropionyl chloride is added dropwise. After 1 hour the solution is neutralized and the dyestuff is obtained by evaporating the solution in vacuo.

The dyestuff dyes cotton covered violet tints.

By acylating the metallisferous azo dyestuffs listed in Column l with ccB-dichloropropionyl chloride or equivalent amounts of rxzB-dibromopropionyl chloride as described in Examples 4and 5 there are obtained dyestuffs that dye cotton the tints shown in Column ll.

1. Copper complex of the dyesturf of the formula 08 I QHJR TA my M L mus-gnarl 33 I Continued I! 2. 122-chrom1um complex of the dyeatutt of the formula -N-zflbluish violet tIO S- 4K 3. 1:2-chromium complex of the dyestuff (H H0 H2N-N= mm reddish blue H0 5 SO H COOH EXAMPLE 6 31.4 parts of 4-(azB-dichloropropionylamino)-lamino-benzene-2-sulfonic acid are dissolved in 600 parts of water with the addition of sodium carbonate. 30 parts of hydrochloric acid of 30 percent strength are added at 0 to 5C, and the mixture is diazotized with parts by volume of 4N-sodium nitrite solution. The diazo suspension, which gives an acid reaction to Congo, is then added to an ice-cold solution of 42.3 parts of l-benzoylamino-S -hydroxy-naphthalene-3:6- disulfonic acid and parts of sodium carbonate in 400 parts of water. On completion of the coupling the dyestuff is salted out with sodium chloride, filtered off and dried in vacuo at 60 to 70C.

The resulting dyestuff of the formula (In ClCH -CHCONHQN=N HO s dyes cellulose by the process described in Example 1 l red-violet tints.

lf desired, the coupling can be carried out with advantage in the presence of sodium acetate or sodium bicarbonate.

The 4-(azfi-dichloropropionylamino)-l aminobenzene-2-sulfonic acid used in this Example can be prepared thus:

18.8 parts of l:4-diaminobenzene-Z-sulfonic acid are dissolved in 400 parts of water, and then neutralized with sodium carbonate. While stirring vigorously, 21 parts of ouB-dichloropropionyl chloride are added dropwise at 0 to 5 in the course of 20 minutes, and at the same time the reaction solution is neutralized with dilute sodium carbonate solution so as to maintain the reaction solution at a pH value of 6 to 7. On completion of the reaction, the whole is acidified with hydrochloric acid, filtered, and the reaction product washed with saturated sodium chloride solution.

In a similar manner 5-(azB-dichloropropionylamino)- HO NHCOO l-aminobenzene-2-sulfonic acid can be prepared from S-amino- 1 -eminobenzene-2-sulfonic acid.

In the following Table further dyestuffs are listed which are obtained according to the process described in Example 6 by coupling the diazotized amines listed in column 1 with the coupling components listed in column 2 and which yield on cotton dyeings having the shades indicated in column 4. In this Table the under lined amino-group means either an a,B-dichloropropionylamino group (1 in column 3) or an a,B-dibromopropionylamino group (11 in column 3). The diazo components corresponding to the indicated capital letters are the following:

A: aniline B: l-aminobenzene-2-sulfonic acid C: l,3-diaminobenzene-6-sulfonic acid 2-aminonaphthalene-4,8-disulfonic acid 1 aminonaphthalene-3,6-disulfonic acid 2-aminonaphthalene-5,7-disu1fonic acid V: 2-amin0naphthalene-6,8-disulfonic acid X: 2-aminonaphthalene-4,6,8-trisulfonic acid Y: Z-aminonaphthalene-l-sulfonic acid.

c wo

Continued l [I III IV I I A l-amino-S- I red I H m N hydroxynaphthalene3,6

disulfonic acid 5 N be d9. I 2) A do u do nzoyIdmino-il-hydroxy- I bluish red 3) B do l d naphthalene-Li 6-disulfonic 4 8 do II d 45) I do. I do. 5) C do. I do. 4 K do I d 6) D do. I bluish-red '1 E dd. l red 43] L 8) E du do 10 44) C I-N-aceiyIamin0-8-hydroxy- I red 9) F d0, l naglhthalene-4,fi-disulfonic IO) F do. ll d ac! I l 0 do 1 2 45) D I-N-acetylamino-8-hydroxy- I bluish-red 2) 6 do N do naphthalene-4,6-disulfonic I3) H (10. I do. and I4) H d0. ii do. J do, 1 red J do. I do. 15 K do. I do. 16) K do I 48) L do. I do. [7) L do 49) C l-N-butyrylamino-B-hydroxy- I do. g M do do 50 D napthaIene-4,6-disulfonic acid l9] M do. II do. 20 A l-amlnD-B- I do, 51 I 1 I hydroxyna hthalene-4,6- 52) K I disuI onic acid 20 L do I do. 2|) A do do 54) C l-N-benzoyIamino-B-h droxy I do. 22) B 1 do naphthalene-4,6-disu fonic 23) B do. II dd. acid 24) C I 55] D ClO. l d0. 25 D do. I bluish-red 561 1 bluish-red 26) E (I0. I red 57) K I 21 E dd. ii d0. 58) P- I 28) F do. I do. 25 59) C l orange 29) F [I do hydroxynaphthalene-7- 30) 0 do I do sulfonic acid 31) 0 do N do 60) C d0. II do. 32) H I do 6| D do. II reddish-orange 33) H do. do red 34) .I do. I do. 30 3;: E 3:: 33: By coupling the diazotised amines listed in column 1 37) M do with the coupling components listed in column 2 of the 23; 2:4 y?: I 3::- following Table further dyestuffs are obtained, which hydroxynapmhalenea'a yield on cotton dyemgs having the shades indicated in disulfonic acid column 3. In I D do. I luish ed this Table the underlined amino group al 4| J do. I red ways means either an a,B-d|chloropropionylaminoor 42 K do. I do. an a,fi-dibromopropionylamino group:

I II n l J 2 2; K ureido 5 hydroxynaphthalene 7 suliggic acid 32 3 L d0. 4) C 2-( N-a B-dichloropropionyI-N-methyl )-amino-S- g: hydroxynaphthalene-7-sulfonic acid 5 I D dO- reddish-orange 6) J do. 7 K do. '3" s L do. 9) C 2-Na,[3-dibromopropionylmethylamino-S-hydroxydo naphihaIene-7-sull'onic acid 1? g 1 g reddish-orange I2) K d: 3 13) L do: 14) B 2-amino-5-hydroxynaphthalene-7-sulfonic acid 3:: g i E 33- reddish-orange I7 0 do 33' :g) I; do. d J do. 20) C Z-N-afi-DichIoropropionylamino-S-hydroxy 2,

8 21 D naphthalene 7 sulfonic acid 22 i J 33: reddisgigorange 53) i do. do. 25) C 2-N-a,B-dibromopropionylamino-S-hydroxydo.

naphthaIene-7-sulfonic acid Oran e D reddish 27 1 do. f 53; if 33' 30) B 2-amino-8-hydroxynaphthalene-fi-sulfonic acid ga g; E reddish-orange :2; a 331 do. d 35) B f1121izndeciilzeyIiiinino 5'1-hydroxynaphthalene-\a-sulorangz-red 36) E d 37) F d8. 3? as o dd. do: 39) H do. do. M do. do

Ill

zzzr-r-rr'r-l-l-i-r-xxxxxxxxxxxRRRRRRRQOOOOOQOOUUUUUUU0066006000600 O OOOOOOOOOOF7 'U Or"7='-U nr-w-U fir'ai -U O 2-a,{3-dichlorpropionylamino-8-hydmxynaphlhulenc- 6-su fonic acid 0. Z-N-a,B-dihrompropionylaminc-8-hydroxynaphlhaleneb-sulfonic acid 0. 2-( N-a.fidichlorpropionyl-N-methylamino )-8-hydroxynaphlhalene-b-sulfonic acid 0. 2-( N-a.B-dihromopropionyl-N-methylamino)-8hydroxynaphthalene-G-sulfonic acid l-hydmxynaphthalin Z-hydroxynaphthalin l'hydroxynaphthaIin-4-sulfonic acid l-hydroxynaphthalin-$-sulfonic acid Z-hydroxynaphthalin-4-sulfonic acid Z-hydroxynaphthalene-6-sulfor|ic acid 2-hydroxynaphthalene-7-sulfonic acid 3-melhyl-S-pyrazolone l-phenyl-3-methyl-5-pyrazolone l-( 3 -a.B-dibromorropionylaminopheny] 3-methyI-5-pyrazo one l-( 4-a.B-dibromopropionylaminophenyl)- S-meIhyI-S-pyrazolone l-phenyI-J-carboxy-S -pyrazolone 3-carboxy-5-plxrazolone Z-aminonapht alene-S-sulfonic acid 2-aminonaphlhalene-fi-sullonic acid 2-aminonaphthaleneJ-sulfonic acid Z-aminonaphthalene-8-sulfonic acid l-aminonaphlhalenei-sulfonic acid l-aminonaphthalene-5-sulfonic acid i-aminonaphthalene--sulfonic acid l-aminonaphthalene-7-sulfonic acid I-aminonaphthalene-B-sulfonic acid Z-aminonaphthalene-S-sulfonic acid 2-aminonaphthalene--sulfonic acid Z-aminonaphthalene-7-sulfonic acid 2-aminonaphthalene-8-sulfonic acid l-aminonaphthalene-4-sulfonic acid l-aminonaphihalcne-5-sulfonic acid l-aminonaphthalene-6-sulfonic acid l-aminonaphthalene-7-sulfonic acid I-aminonaphthalene-B-sulfonic acid 2-aminonaphthalene-S-sulfonic acid Z-aminonaphthalene-6-sulfonic acid 2-aminonaphthalene-7-sulfonic acid Z-aminonaphthalene-S-sulfonic acid 1-aminonaphthaIene-4-sulfonic acid l-aminonaphthalcne-S-sulfonic acid 1-aminonaphthalene-fi-sulfonic acid l-aminonaphthalene-7sulfonic acid 1-aminonaphlhalene-S-sulfonic acid Z-aminonaphthalcnc-S-sulfonic acid 2-aminonaphthalene-fi-sulfonic acid 2-aminonaplithaleneJ-sulfonic acid Z-aminonaphthalene-S-sulfonic acid I-aminonaphlhalene-4-sulfonic acid I-aminonaphthalene-S-sulfonic acid l-aminonaphthalene-b-sulfonic acid I-aminonaphlhalene-7-sulfonic acid l-aminonaphthalene'8sulfonic acid 2-aminonaphlhalene-S-sulfonic acid 2-aminonaphthalene-fi-sulfcnic acid 2-aminonaphlhaleneJ-lulfonic acid 2-amincnaphlhalene'8-lulfonic acid l-aminonaphthalene-i-lull'cnic acid l-aminonaphlhalenc-S-sulfonic acid l-aminonaphthalene-(i-sulfonic acid l-arninonaphthalene-7-sulfonic acid l-aminonaphthalene-S-suli'onic acid Z-aminonaphthalene-S-sulfonic acid 2-aminonaphthalene'6-sulfonic acid Z-aminonaphthalene-7-sulfonic acid Z-aminonaphthalene-S-sulfonic acid 1-aminonaphthalene-4-sulfonic acid 1-aminonaphthaIene-S-suli'onic acid I-aminonaphthalene-b-sulfonic acid l-aminonaphihalene-I-sulfonic acid l-aminonaph!halene-S-sulfonic acid 2-aminonaphthalene-S-sulfonic acid 2-aminonaphthalene-fi-sulfonic acid Z-aminonaphthalene-7-sulfonic acid orange red scarlet do. do. reddish-orange red scarlei do. do. reddish-orange red scarlet do.

0. reddish-orange red scarlet e ow y do.

orange ssiass-s-asss 

1. THE 1.2 OR 1:1 CHRONIUM COBALT OR COPPER COMPLEX OF A MONOAZO DYESTUFF CONTAINING AT LEAST 2 AND AT MOST 3 SULFONIC ACID GROUPS WHICH DYESTUFF CORRESPONDS TO THE FORMULA
 2. A monoazo dyestuff containing at least two and at most three sulfonic acid groups of the formula
 3. A monoazo dyestuff containing 2 or 3 sulfonic acid groups and corresponding to the formula
 4. The monoazo dyestuff as claimed in claim 2 of the formula
 5. The monoazo dyestuff as claimed in claim 2 of the formula
 6. The monoazo dyestuff as claimed in claim 2 of the formula
 7. The monoazo dyestuff corresponding to the formula 